Process of extracting bromine



2 Sheets Sheet 1.

(No Model.)

H. H. DOW. PROCESS OF EXTRAGTING BROMINE.

No. 460,370. Patented Sept.- 29, 1891.

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(No Model.) 2 Sheets-Sheet 2.

H., H. DOW.

PROCESS OF EXTRAGTING BROMINE.

No. 460,370. Patented Sept. 29,1891.

Wt wmsksms I Iva/rand?) r UNITED STATES PATENT OFFICE.

HERBERT II. DOV, OF CLEVELAND, OHIO.

PROCESS OF EXTRACTING BROMINE.

SPECIFICATION forming part of Letters Patent No. 460,370, datedSeptember 29, 1891. Application filed October 23, 1889. Serial No.328,366. (No specimens.)

To (ZZZ whom it may concern.-

Be it known that I, HERBERT H. DOW, of Cleveland, in the county ofGuyahoga and State of Ohio, have invented a certain new and usefulProcess of Extracting Bromine from Natural Brine or Bitter Waters and Ido hereby declare the followingto be a full, clear, and exactdescription of the invention, such as will enable others skilled in'theart to which it pertains to make and use the same.

My invention relates to a new process of extracting bromine from naturalbrine or from bitter water, as the case may be; and it consists in thesteps hereinafter described and claimed. Many salt-wells will not payfor Working for salt, owing to the low price of thelatter commodity. Thebrine from some of these wells is rich in bromine, and it is a matter ofmuch commercial value to be able to cheaply recover the bromine from thebrine without incurring the expense of evaporating the water of thebrine; and my improved process has this end in view, although theprocess is equally well adapted to working bitter waters where the brinehas been worked for salt.

My process, in brief, consists, first, in setting the bromine free fromits chemical combinations in the brine, and this may be done by variousmeans-for example, by electricity, or by the agency of chlorine gas, orby introducing into the brine the equivalents of chlorine gas, to wit:first introducing sulphuric acid, followed by the ordinarybleaching-powder of commerce. By means either of electricity, chlorinegas, or of the aforesaid chemicals the bromine is set free from itschemical combination, leaving the bromine in solution in the brine;second, the bromine is recovered from its soluble condition in the brineby means of air-currents brought in contact with the brine, the brominebeing absorbed and carried away by the air, and subsequently the bromineis recovered from the air by bringing such bromine-laden air in contactwith such substance as Will readily form a chemical combination withvthe bromine. For instance, by passing such bromine-laden air through abody of iron-turnings the bromine and iron will chemically unite,forming bromide of iron, known as ferric bromide, which, with themoisture simultaneously absorbed from the air, will form a solution, andsuch ferric-bromide solution is an article of commerce and may beshipped in such condition. ship the bromine in solid condition it maybeconverted into ferrous bromide, which is a more staple compound whenheated than the ferric bromide by bringing the aforesaid solution incontact with iron, and subsequently evaporizing it to dryness in avessel from which the air is excluded by steam or by other means, theproduct being a solid, (FeBr,.) In place of the iron-turnings aforesaidfor recovering the bromine from the air by substituting other metals orsubstance having an affinity for the bromine, other compounds of brominemay be had-such, for instance, as bromide of zinc, bromide of copper,calcium bromide and bromate, sodium bromide and bromate, &c. Also, otheraeriform bodies other than recovering the bromine from the brineforinstance, natural or artificial gas-where these may be had at smallcost; but this must not be confounded With the use of chlorine gas inthe first stages of the process for setting the bromine free from thechemical combination in the brine.

In the accompanying drawings is illustrated suitable apparatus forcarrying out my invention, although such apparatus may be varied almostindefinitely, Figure l is an end elevation in section. Fig. 2 is anelevation in transverse section taken through the center of theapparatus employed in the latter stages of the process.

A are storage-tanks for the brine and in which the brine is treated byelectricity or with chlorine gas or by chemicals that are substantiallythe equivalents of chlorine gasfor instance, sulphuric acid and commonbleaching-powder for freeing the bromine from itschemical combinationsin the brine, and this is usually done in one storage-tank at a time.After such treatment the brine is drawn off into a shallow tank B, andduring the drawing off of the one storage-tank probably the brine inanother storage-tank Will be undergoing the treatment just referred to.Meanwhile possibly a third tank is filled with brine, so that theprocess may be continuous. Tank 13 is preferably located in a closedroom 0 near the upper portion thereof, this tank In case it is desiredto atmospheric air may be used for 40 process goes on.

B having a series of drip-holes, from which the brine is showered downpreferably upon sheets of burlap stretched upon frames in the inclinedposition shown. In place of bur- 5 lap wooden surfaces may be employed;but

the burlap is preferable on account of the greater surface exposed tothe air.

D is a blower for furnishing the air that is circulated through room 0,the dischargepipe D of this blower entering, as shown,

mine and the fresh air absorbs this remnant of bromine almost to thelast degree. As the air passes upward it comes in contact with brinericher with bromine, and at last comes in contact with the brine that isshowered down, containing its full amount of bromine,

and hence the air in passing off through opening 0 has been laden withbromine to its full extent. The air passes off through duct d and isconducted through the bottom of container E, this container beingpartially filled for instance, with iron-turnings or scrap-iron, inwhich case the bromine uniting with the iron will form bromide of iron,known as ferric bromide, and simultaneously therewith the moisture ofthe atmosphere will be absorbed by the ferric bromide forming asolution, and this ferric-bromide solution drips down and is dischargedthrough spout e into vessel F, the latter being preferably of stone.Vessel is covered and the exhaust-pipe of the blower connects with thisvessel. Hence the air of this vessel, after passing the iron and havingbeen freed from the bromine, is again returned to the bottom of room 0,and so the In case other than atmospheric air is used-such, forinstance, as natural or artificial gas-the operation is the same. Thelower floor of the room is shown inclined, with the discharging-spout Gin the 5 form of a trap for drawing off the waste brine without wastingthe air.

If, in place of iron, other substance having a strong affinity forbromine be introduced into vessel E, other compounds of bromine will ofcourse be formed.

The specific compound of bromine that is formed is of secondaryimportance, the main object being to get the bromine in someconcentrated form, from which by subsequent processes the variousbromides used in the arts can be made.

For reducing the ferric-bromide solution aforesaid to ferrous bromidethe liquid from container F is poured into tower L, the lat- 6o terbeing filled with .iron turnings, scrap, or

iron in some form. The tower terminates in a tube 1, discharging intovessel H. This vessel has a steam-jacket II for heating the vessel, andhas a removable cover H together with the usual appliancesforherme'tically sealing the vessel and steam-jacket. A steam-pipe itleads into the steam-space of the jacket. The pipe 71' leads into vesselH, near the top of the latter, this latter pipe having a suitablecheck-valve 712, that allows vapor to escape from the vessel,butprevents the ingress of air from the outside. The ferric bromide as itpercolates through the iron in tower L absorbs more iron, thusconverting the product into ferrous bromide, this liquid beingdischarged into vessel H, the latter being filled with an atmosphere ofsteam produced by boiling a quantity of water in the vessel, so as toexpel the air previous to the introduction of the ferrous bromide. Thislatter solution is boiled to dryness and afterward allowed to cool. The

cover of the vessel is then removed and the solid product is takenout'of the vessel, the air having no decomposing effect on the solid dryproduct.

I am aware of United States Letters Patent, Reissue No. 3,47 9, grantedto Amalie Stieren' June 1, 1869; but in the process therein describedfor obtaining bromine there is no mention of gas of any kind, exceptchlorine gas, used for the purpose of freeing the bromine from itschemical combination in the brine, and there is nothing said ofemploying atmospheric air or gas of any kind to recover the bromine thusset free, and there is nothing in the patent that would even. suggestthe same.

What I claim is 1. The process herein described of extracting brominefrom brine or bitter water and reducing the product to a solid bromide,consisting, first, in freeing the bromine from its chemical combination;second, separating the bromine from the brine by means of an air-blast;third, forcing the bromine-laden air through a metal or substance thatwill combine with the bromine, thus producing a bromide, and finallyboiling the latter to dryness out of contact with the air, substantiallyas set forth.

2. The improvement in the art ofobtaining bromine from naturalsalt-water, which'consists in heating such salt-water to set the brominefree from its chemical combination, then separatingthe freed brominefrom the saltwater by means of an air-blast, and finally absorbing thebromine from the air with suitable absorbing material.

In testimony whereof I sign this specification, in the presence of twowitnesses, this 12th day of October, 1889.

HERBERT H. DOIV.

Witnesses:

O. H. DORER, S. G. NOTTINGHAM.

